Alpha-olefin interpolymers formed with unsaturated organo silanes

ABSTRACT

The preparation of interpolymers of ethylene by interpolymerization of ethylene, an unsaturated organo silane and a monoolefin and with or without a polyene in the presence of a Ziegler type catalyst, particularly to produce uniquely modified polymers from the post-reaction between nucleophiles and the hydrolyzable groups that remain attached to the silicon atom in the interpolymer.

United States Patent 11 1 [11] 3,

Bond, Jr et a1. Oct. 9, 1973 ALPHA-OLEFIN INTERPOLYMERS 3,198,766 8/1965Nitzche et al 260/46.5 UA FORMED WITH UNSATURATED ORGANO 3,444,1345/1969 Soldatos 260/47 UP SILANES 3,644,306 2/1972 Long1 et al 260/80.7l3,577,399 5/1971 Mortimer 260/88.l [75] Inventors; William C, Bond, Jr;Harold J, 3,375,236 3/1968 Vande Castle 260/80.71

Wahlborg, both of Baton Rouge, L FOREIGN PATENTS OR APPLICATIONS [73]Assignee: p y Rubber & Chemical 1,001,838 8/1965 Great Britain 260/80.71

Corporation, Baton Rouge, La. Primary Examiner-William H. Short 22 Fl(1. 17 1971 1 I e June Assistant Examiner-Edward Woodberry [21] Appl.No.: 154,196 Att0rneyMcDougall, Hersh & Scott [52] U.S. Cl. 260/80.71,117/161 ZA, 260/25,

260/l7.4 oc, 260/41 0, 260/Sl, 260/46.5 [57] ABSTRACT 260/58? Thepreparation of interpolymers of ethylene by inter- 51 I t Cl C08f 15/04polymerization of ethylene, an unsaturated organo sii 71 88 l R lane anda monoolefin and with or without a polyene 1 w g C 41 I in the presenceof a Ziegler type catalyst, particularly UA to produce uniquely modifiedpolymers from the postreaction between nucleophiles and the hydrolyzableReferences Cited groups that remain attached to the silicon atom in theinter o1 mer. UNITED STATES PATENTS p y 3,177,166 4/1965 Gregory 260/47UP 27 Claims, No Drawings ALPHA-OLEFIN INTERPOLYMERS FORMED WITHUNSATURATED ORGANO SILANES The invention relates to new and improveda-olefin interpolymers and to methods for the preparation of same andmore particularly to the preparation of new and improved vulcanizablea-olefin interpolymers having a number of unique properties andcharacteristics.

It is an object of this invention to produce and provide a method forproducing interpolymers of ethylene, an unsaturated organo silane andolefinic compounds which then utilize the hydrolyzable groups on thesilane portion of the interpolymer in a post-polymerization reaction toform a variety of interesting and uniquely modified interpolymers whichcannot be formed directly during the polymerization. These modifiedinter polymers have many novels applications and properties not normallyassociated with ethylene interpolymers.

The interpolymers of this invention are prepared by theinterpolymerization of a first monomeric component in the form ofethylene, and a second monomeric component in the form of an unsaturatedorgano silane having the general formula R SiX in which X is a highlyhydrolyzable group other than an oxygen containing group, as representedby a halogen such as chlo-. rine, bromine or iodine, a tertiary aminogroup, and the like, R is a group selected from the group consisting ofhydrogen, an organic aliphatic group such as methyl, ethyl, propyl,isopropyl, butyl, amyl, hexyl, octadecyl, and the like C -Chydrocarbons, an organic alicyclic group such as cyclopentyl, cyclohexyland the like, an

aryl or alkaryl group such as phenyl, monoand polyalkyl phenyls such astolyl, xylyl, mesitylyl, mono-, diand triethyl phenyls, naphthyl,monoand polyalkyl naphthyls such as methyl naphthyl, diethyl naphthyl,etc., and anthracyl, and aralkyl group such as benzyl, Z-phenylethyl,and the like, a heterocyclic radical, and in which at least one of the Rgroups is an organic group having at least one carbon-to-carbon doublebond, such as allyl, vinyl and the like, and in which the unsaturatedorganic group is preferably a norbornenyl or alkyl substitutednorbornenyl group, and in which said groups may be substituted orunsubstituted, halogen substituted or unsubstituted, and in which n is anumber of from 1 to 3, and a third monomeric component in the form ofmonoolefins, preferably an a-monoolefin containing from 3 to 20 carbonatoms, and preferably 3 to carbon atoms, as represented by the preferredcomponent propylene. If desired a fourth monomeric component in the formof a polyene may also be included.

The silicon containing compounds as mentioned above are usually calledunsaturated organosilanes but they can also be called silyl substitutedolefins depending on the complexity of the organic substituents on thesilicon atom. It will be noted later that the nomenclature has followedthe organosilane precedent when discussing simple silicon substitutedolefins but when specific norbornene compounds were mentioned thesilylorganic type nomenclature has been used.

It will be understood that the second monomer may comprise one or amixture of unsaturated organosilanes of the type described and that thethird monomeric component may be formed of one or more olefins havingfrom 3 to carbon atoms and that the fourth monomer in the form of apolyene may constitute one or a number of polyenes of the types whichwill hereinafter be described in greater detail.

The second monomer or group of monomeric compounds, identified as anunsaturated organosilane, may be represented by the general formulaR,,SiX in which n is a number from 1 to 3, X is a highly hydrolyzablegroup such as a halogen group, a tertiary amino group and the like, andR is hydrogen or an organic group as previously described, in which atleast one of the R groups is an organic group containing one or moreolefinic groups, in which the second monomer may be represented by suchcompounds as vinyltrichlorosilane, allyltrichlorosilane,vinyldichlorosilane, allylmethyldichlorosilane,allyldimethylchlorosilane and the like; an unsaturated aryl or alkarylsilane such as styryltrichlorosilane and the like, but it is preferredto make use of a silane in which an unsaturated organo group on thesilicon atom is a norbornenyl group as represented by5-trichlorosilyl-2-norbornene, 5- methyldichlorosilyl-Z-norbornene 5-dimethylchlorosilyl-2-norbornene 6-methyl-5-trichlorosilyl-2-norbornene, 7-methyl-5-trichlorosilyl- 2-norbornene,5-trichlorosilylmethyl-2-norbornene, 5-phenyldichlorosilyl-2-norbornene,5-tribromosilyl-2- norbornene, 6-chloro-5-trichlorosilyl-2-norborneneand 5,6-bis(trichlorosilyl)-2-norbornene.

The third'monomeric compound can be an a-olefin having from 3 to 20carbon atoms and may be represented by the general formula R Cl-l CHwherein R is a C to C alkyl radical which may be branched or straightchained, halogen substituted or unsubstituted, and which may berepresented by the compounds propylene, l-butene, l-pentene, l-hexene,l-heptene, 1- octene, l-nonene, l-decene, 4-methyl-l-pentene,4-methyl-1-hexene, 4,4-dimethyl-l-pentene, S-methyll-heptene,6-methyl-1-heptene, etc. The third monomeric component may also be amono unsaturated bridged ring hydrocarbon or halogenated bridged ringhydrocarbon such as the derivatives of bicyclo (2,2,1) heptene. Specificexamples of preferred bridged ring compounds of this type arenorbornene, 5-chloro-2- norbornene, 7,7-dimethyl-2-norbornene,5-ethyl-2- norbornene and the like.

The polyene or other ethylenically unsaturated compound containing aplurality of carbon-to-carbon double bonds may be an open chainpolyunsaturated hydrocarbon containing 4 to 20 carbon atoms, such as1,4-hexadiene, monocyclic polyenes and polycyclic polyenes, but it ispreferred to make use of a polyunsaturated bridged ring hydrocarbon,such as the polyunsaturated derivatives of bicyclo (2,2,1) heptanewherein at least one of the double bonds is present in one of thebridged rings, such as dicyclopentadiene, bicyclo(2,2,l)hepta-2,5-diene, or alkylidene norbornenes and preferably a5-alkylidene-2-norbornene wherein the alkylidene group contains from oneto 20 carbon atoms and preferably one to eight carbon atoms, or thealkenyl norbornenes, and preferably the 5-alkenyl-2-norbornenes whereinthe alkenyl .group contains from three to 20 carbon atoms and preferablyfrom three to 10 carbon atoms. Other bridged ring hydrocarbons includepolyunsaturated derivatives of bicyclo (2,2,2) octane, as represented bybicyclo (2,2,2) octa-2,5-diene, polyunsaturated derivatives of bicyclo(3,2,1) octane, polyunsaturated derivatives of bicyclo (3,3,1) nonane.At least one double bond is present in the bridged ring of the abovecompounds and at least one other double bond is present in a bridgedring or in a side chain. Specific examples of preferred bridged ringcompounds of the type described above include S-methylene-Z-norbornene,5-ethylidene-2-norbornene, 5-n-propylidene-2- norbornene,6-isopropylidene-Z-norbornene, 5-n-butylidene-2-norbornene,6-isobutylidene-2- norbornene, 5-(2-methyl-2-butenyl)-2-norbo rnene, 5-(3-methyl-2-butenyl)-2-norbornene v and 5-(3-dimethyl-4-hexenyl)-2-norbornene. The interpolymer prepared from5-ethylidene-2-norbornene is greatly preferred since the combinationwhich makes use thereof has outstanding properties and it appears to besomewhat unique by reference to the others.

The fourth monomeric component, the polyene or substituted polyene, maybe chemically bound in the interpolymer in an amount within the range of0.1 to 10 mole percent, and preferably 0.1 to 3 mole percent, or in anamount to provide an actual or calculated unsaturation level of at leasttwo double bonds per 1,000 carbon atoms of the interpolymer chain.However, amounts to provide much higher unsaturation levels arepreferred, such as levels of up to 100 double bonds per 1,000 carbonatoms in the interpolymer, and preferably an amount to provide from 2.5to 30 double bonds per 1,000 carbon atoms, and more preferably 2.5 todouble bonds per 1,000 carbon atoms. The specific unsaturation levelselected to be introduced by the polyene component will vary dependingupon the properties desired in the elastomeric interpolymer that isformed.

The unsaturated organo silane, or second monomer, is employed in thereaction mixture in an amount within the range of more than 0.1 percentbut less than 10 percent by weight and preferably in an amount withinthe range of 1.0 to 5.0 percentby weight of the total monomer system.

Since the allyl and vinyl and the like unsaturated aliphatic halosilanes are slow in the polymerization reaction by comparison with thenorbornenyl silanes and are less competitive from the standpoint ofreactivity by comparison with the other monomeric components, more ofthe aliphatic unsaturated silane is used, but only a fraction, such asone-hundredth to one-tenth of the monomer, it is believed, enters intothe polymer backbone. On the other hand, the norbornenyl or substitutednorbornenyl silanes. are sufficiently reactive to compete more favorablywith the other monomer components and therefore are preferred for use asthe second monomer.

As the second monomer, it is undesirable to make use of an unsaturatedsilane in which the highly hydrolyzable groups are in the form of analkoxy or primary or secondary amino groups, such as methoxy or ethoxyor NHR groups, since such oxygen and nitrogen containing groups tend topoison the polymerization catalyst and thus destroy the reactivitynecessary for interpolymerization of the monomers. When use is made ofunsaturated silanes having highly hydro lyzable halogen or tertiaryamino groups as the hydrolyzable groups on the unsaturated silane, suchgroups can be retained by the second monomer during interpolymerizationwith the other monomers to become a part of the backbone of theinterpolymer.

The interpolymerization of the monomeric components described can becarried out in solution in an inert organic solvent, in the presence ofa Ziegler type catalyst, all of which will hereinafter be described.

In the interpolymer of the invention, it is preferred to make use of thefirst monomer ethylene and the third monomeric component propylene orother C to C monoolefin for copolymerization in the interpolymer in theratio of 20-95 moles of ethylene to -5 moles of the third monomericcomponent and preferably within the range of 45-90 moles of ethylene to55-10 moles of propylene, or other third monomeric component.

The polymerization solvent may be any suitable inert organic solventwhich is liquid under the reaction conditions such as any prior artsolvent useful for solution polymerization of monoolefins in thepresence of Ziegler type catalysts. Examples of satisfactory hydrocarbonsolvents include acyclic paraffins and olefins containing three to eightcarbon atoms, and preferably hexane; aromatic hydrocarbons andpreferably aromatic hydrocarbons containing a single benzene nucleussuch as benzene, toluene and the like; cyclic hydrocarbons which have aboiling point range approximating that for the straight chain paraffinhydrocarbon and aromatic hydrocarbons discussed above, and preferablycyclic hydrocarbons containing five or six ring carbon atoms;chlorinated hydrocarbons such as carbon tetrachloride, chlorobenzene andtetrachloroethylene. The solvent may be a mixture of one or more of theforegoing hydrocarbons, such as a mixture of aliphatic and naphthenichydrocarbons, preferably having approximately the same boiling range asnormal hexane. It is important for the solvent to be dry and free ofsubstances which will interfere with the Ziegler catalyst to be used inthe polymerization process.

Ziegler catalysts, as described in the prior art, may be employed. SuchZiegler catalysts are disclosed in a large number of patents, such asUS. Pat. No. 2,933,480, NO. 3,093,620, No. Nos. No. 3,211,709 and No.2,1 13,1 15. Such Ziegler catalysts generally include metal organiccoordination catalysts prepared by contacting a compound ofa heavy metalof the groups IV-b to VII-b of the Mendelejeff periodic system ofelements, such as titanium, vanadium and chromium halides with anorgano-metallic compound of a metal of Groups I to II! of theMendelejeff periodic system which contains at least one carbon-metalbond, such as trialkyl aluminum and alkyl aluminum halides wherein thealkyl groups contain from one to 20 and preferably one to four carbonatoms.

The preferred Ziegler catalyst for the described polymerization isprepared from a vanadium compound and alkyl aluminum halide such asvanadium trichloride, vanadium tetrachloride, vanadium oxychloride,vanadium acetylacetonate, etc., and alkyl aluminum chloride activatorshaving the general formula R,AlCl, and R AlCl, and the correspondingsesqui-chlorides having the general formula R Al Cl in which R ismethyl, ethyl propyl, butyl, or isobutyl. In the catalytic system, thealuminum to vanadium mole ratio of the aluminum and vanadium compoundsmay be within the range of 5-200:l and preferably within the range of15-60:1. A catalyst prepared of alkyl aluminum sesquichloride, such asmethyl or ethyl aluminum sesquichloride, and vanadium oxychloride ispreferred, with the preferred ratio of 1 mole vanadium oxychloride for5-200 moles of aluminum and preferably for each 15-60 moles of aluminum.

Generally the polymerization reaction may be carried out in atemperature range of 40 to 150 C and preferably within a temperaturerange of 0 to 60 C during the course of the reaction. The polymerizationreaction may be carried out at substantially atmospheric pressure butpressures up to 1,000 psi may be employed.

The polymerization is preferably carried out on a continuous basis in adry reaction vessel which is closed to the outside atmosphere and whichis provided with means for agitation, reactor cooling means, and inletsand outlets for continuously supplying the ingredients of the reactionmixture including the monomer and catalyst, and for continuouswithdrawing of the elastomer solution. The polymerization is carried outin a liquid phase in the organic solvent in the presence of the Zieglercagalyst and the solution of elastomer in the polymerization solvent iswithdrawn continuously from the reaction vessel and the cement is thentreated with the desired chemical hereinafter described which will reactwith the hydrolyzable Si-X function to form the uniquely substituteda-olefin interpolymer.

The chemical agents used in the post-reaction with the hydrolyzableSi-Cl or R b1-N groups are usually of a nucleophilic nature. Typicalchemical groupings are R-OH, R NH, R-SH and where R can be alkyl oraryl, or where the alkyl or aryl group is substituted withnonprotonaceous substituents such as cyano, aldehydo, keto, tertiaryamino, alkoxy and halo. Also certain highly hindered portonaceoussubstituents such as tertiary alcohols, substituted amines, andsubstituted phenols may be present on the R group.

It is further to be noted that mixtures of post-treating agents can beused. Also, in some cases it may be advantageous to use two agents inseries because certain agents react very slowly with the hydrolyzableSi-X moiety so that only partial interactions take place to leave Si-Xsites which upon workup of the polymer will form Si-O-Si'crosslinks togive an intractable, crosslinked interpolymer. Therefore, to avoidcrosslinking, the residual Si-X groups are terminally treated with amore active agent such as a primary alcohol, preferably methanol, tocompletely remove crosslinking sites from the modified interpolymer.

Typical post-treatment agents are alcohols such as methanol, ethanol,allyl alcohol, benzyl alcohol, crotyl alcohol 2,2,2-trichloroethanol,2-cyanoethanol, diacetone alcohol, 4-hydroxy-3,S-di-t-butylbenzylalcohol, N,N-dimethylethanolamine and the like; amines such asdimethylamine diethylamine, methyl benzylamine and the like; mercaptanssuch as methyl mercaptan, butyl mercaptan and the like; anhydrides suchas acetic anhydride, maleic anhydride, itaconic anhydride, phthalicanhydride and the like.

Any interpolymers of the invention which contain residual unsaturationmay be cured in accordance with prior art procedures. As a general rule,a curing procedure which is normally followed in curing unsaturatedhydrocarbon rubbers, such as styrene-butadiene rubber, natural rubber,polybutadiene rubber, synthetic polyisoprene rubbers and the like, willbe satisfactory. Use may be made of various curing agents in effectingthe rapid cure of the interpolymer.

vulcanization may be achieved with the use of the usual vulcanizingagents such as sulphur, or sulphur bearing compounds which providesulphur under the vulcanizing conditions. Sulphur is the preferredvulcanizing agent and it is usually used in an amount of about 0.5 to 3parts by weight per 100 parts by weight of the rubber. Zinc oxide andother metal oxides may be used in an amount of, for example, about 2 to10 parts by weight per 100 parts by weight of rubber.

Conventional fillers and pigments may be formulated with theinterpolymer, such as 10 to 400 parts by weight of carbon black, finelydivided silica, esterified silica, titanium dioxide, kaoline andWhiting, per 100 parts by weight of rubber. It is also possible toextend the interpolymer with oil such as extender oils as represented bynaphthenic oils usually added in an amount of 10 to 300 parts andpreferably 20 to parts per parts by weight of rubber.

vulcanization is accomplished by heating the compounded interpolymer ata vulcanizing temperature for a period of time sufficient forvulcanization, such as at a temperature above C for 10 to 90 minutes,and preferably within the range of 180 C for about 30 minutes.

When carrying out a free radical cure of the interpolymer and compoundsformed thereof, a heat activated free radical curing agent is admixedwith the interpolymer and the mixture is heated to a sufficiently hightemperature to activate the curing agent for cure over a practicalperiod of time. Usually temperature of 50 to C for a period of severalminutes to several hours is sufficient. Preferred free radical curingagents include organic peroxides such as dicumene hydroperoxide,dibenzoyl hydroperoxide, cumene hydroperoxide andditertiarybutylperoxide.

The uncured polymers of this invention may be used in a wide variety ofapplications where the plastic homopolymers and copolymers of ehtyleneare generally used, such as wire coatings, toys, bottles and the like.

The cured polymers and compounds of this invention may be used in a widevariety of articles including tires, belts, hose, tubing and the like.

Having described the basic concepts of the invention, the followingexamples are given by way of illustration, but not by way of limitation,of the practice of the various concepts of this invention.

EXAMPLE 1 This example illustrates the preparation of an EPDM A dry,7-ounce flask containing 100 cc of dry hexane was flushed with nitrogengas and was fitted with a selfsealing syringe cap. The hexane wasflushed with propylene and then pressured to 15 pounds per square inchwith propylene. The flask was brought to 25 pounds total monomerpressure by addition from a feed tank containing 65 mole percentethylene and 35 mole percent propylene. The polymerization was performedin a 35 C water bath. To the flask was added 0.02 mM of butylperchlorocrotonate, 0.05 mM trichlorosilyl-2-norbornene, 0.15 mM ofethyl aluminum sesquichloride and 0.00375 mM of vanadium oxychloride. Asthe polymerization proceeded, the monomer composition was maintainedconstant by continual addition from the feed tank. At 300 and at 600seconds, the above reactants were again charged to the flask. At 900seconds the polymerization was stopped by treating the cement with oneml of water. Irganox 1010, a pentaerythritol ester having the generalformula (an antioxidant of Geigy Chemical Company) was added. At thistime, the solution became thick and jelly like and polymer started tocome out of solution. The polymer was recovered by steam coagulation anddried in a vacuum oven at 75 C. The resulting polymer (5.0 g) wasextremely tough and did not press into a film in a Carver press at 180 Cdue to the siloxane crosslinkmg.

EXAMPLE 2 Example 1 was repeated except that the-trichlorosilyl-Z-norbornene was substituted by an equivalent amount ofa silane having the formula R'SiR,.X in which n is l or 2, R is anorbornenyl or an alkyl substituted norbornenyl of the type previouslydescribed, R is an alkyl or halogen substituted alkyl group such asmethyl, ethyl, n-propyl, isopropyl, npentyl, trichloromethyl,2,3-dibromopropyl, or trichloromethylpropyl, or an aryl, phenyl, oralkaryl or a halogen substituted arylphenyl or alkaryl group, aspreviously described, and X is a highly hydrolyzable group such ashalogen, or tertiary amino group.

The unsaturated silane, identified as the second monomer, is believe toenter into the interpolymerization reaction with the other monomersthrough the unsaturated carbon-to-carbon linkage of the organic groupthat is attached to the silicon atom. Under such circumstances, theorgano silicon component, which forms a part of the interpolymerbackbone molecule, continues to retain the 1 to 3 highly hydrolyzablegroups, such as the chlorine, bromine, tertiary amino groups and thelike. The highly hydrolyzable groups, present on the organo siliconsegment of the interpolymer, remain hydrolyzable and highly reactive inthe formed interpolymer.

Novel concepts of this invention reside not only in the new and improvedinterpolymer that is formed and in its method of manufacture, but alsoin the further processing of the highly hydrolyzable groups of theinterpolymer from which a number of new an novel compositions andproducts can be prepared as well as the method for the manufacture ofsame. For example, primary alcohols, when reacted with the interpolymer,as by addition to the cement, are effective to substitute the OR groupof the alcohol for the hydrolyzable group. Such substituted OR groupingsare not readily hydrolyzable in water or other active hydrogencontaining materials so that the reacted interpolymer can subsequentlybe treated in aqueous medium without crosslinking and the like. Thisenhances the handling of the interpolymer where otherwise the reactionwith water or other active hydrogen containing materials results inthree-dimensional intractable, crosslinked interpolymers, as shown inExample 1.

Suitable primary alcohols can be represented by the general formula R CHOH in which R is hydrogen or a C -C straight or branched chain,saturated or unsaturated, substituted or unsubstituted alkyl or arylhydrocarbon such as methanol, ethanol, allyl alcohol, neopentyl alcohol,benzyl alcohol, crotyl alcohol and the like.

The following example will illustrate the treatment of the interpolymerwith a primary alcohol to produce a noncrosslinked interpolymer.

EXAMPLE 3 Polymerization was carried out as in Example 1 except thatinstead of stopping the polymerization with water, the polymerizationwas stopped with 2 cc of methanol. After reacting with the methanol forabout one hour, the polymer cement was washed with water withoutnoticeable crosslinking. The product was recovered by steam coagulationand dried in a vacuum oven at C. The resulting polymer was soft andpliable and could be pressed to a smooth thin film, between the platesof a Carver press under the conditions as in Example 1.

When the alcohol with which the interpolymer of this invention istreated is an unsaturated alcohol, as represented by the general formulaROH in which R is represented by the formula R-CH=CH-R-CH in which R ishydrogen or a C -C substituted or unsubstituted hydrocarbon in the formof an aliphatic, aryl, alkaryl, heterocycle or other ring structure,such as allyl alcohol, crotyl alcohol, undecenyl alcohol, norbornenylalcohols and the like, the OR grouping, which substitutes for thehydrolyzable groups attached to the silicon atom in the interpolymerchain, adds unsaturated or olefinic sites to the interpolymer to enhancecure or sulphur vulcanization of the interpolymer.

This same concept for introducing unsaturated olefinic groups for cureof the interpolymer by reaction of an unsaturated alcohol forsubstitution of the hydrolyzable groups attached to the silicon atom ofthe interpolymer can also be employed as a means for achieving cure orsulphur vulcanization of ethylene-propylenesilane interpolymers in theabsence of the polyene fourth monomer. For this purpose, theinterpolymer is prepared in the usual manner of the monomers ethylene, amonoolefm containing from three to 20 carbon atoms, preferablypropylene, and an unsaturated organo silane of the type previouslydescribed, in the same ratios, the same catalysts and the sameconditions previously described for preparation of the interpolymer, andthen reacting the formed interpolymer with an unsaturated alcohol tosubstitute the unsaturated OR group of the alcohol for the hydrolyzablegroup attached to the silicon atom in the interpolymer, thereby toincorporate unsaturated groupings into the interpolymer to produce acurable or sulphur vulcanizable compound.

The following example will illustrate the treatment to react theinterpolymer with an unsaturated alcohol to produce a sulphur curablerubber;

EXAMPLE 4 Polymerization was carried out as in Example 1 except that tothe flask there was added 0.03 mM of butyl perchlorocrotonate, 0.04 mMof pyridine, 0.375 mM of nonbornenyl trichlorosilane, 0.3 mM of ethylaluminum sesquichloride and 0.0075 mM of vanadium oxytrichloride. As thepolymerization proceeded, the monomer composition was maintainedconstant by continual addition from the feed tank. At 300 seconds andagain at 600 seconds, the above reactants were again charged to theflask. At 900 seconds, 0.3 cc of pyridine and 4 cc of allyl alcohol wereadded. The flask was agitated for two hours and charged with 4 cc ofmethanol. After 20 minutes of agitation, 1 cc of water and 0.005 gram ofIrganox 1010 were added. The flask was vented and the contents blendedwith water to remove catalyst residues.

The polymer was recovered by precipitation from solution withisopropanol and redissolved in hexane. After recoagulation withisopropanol, the polymer was dried in vacuum at 80 C. The resultingpolymer (4.2 grams) was gel-free and analyzed to contain 1.7 C=C/ 1000C, as determined by titration with bromine.

EXAMPLE 5 The procedure is the same as that of Example 4 except that 4mM of 5-ethylidene-2-norbornene is added with the perchlorocrotonate,norbornenyl trichorosilane and catalyst to produce the tetrapolymer ofthis invention followed by treatment with allyl alcohol to substitutethe allyl group for hydrolynzable halogen groups attached to the siliconatom of the interpolymer to produce a sulphur curable rubber having morethan 5 C=C/l000 C, as determined by titration with bromine.

By way of further medication, the alcohol reacted with the interpolymerof this invention can be one or more halogen substituted alcohols inwhich the R group in the foregoing general formula is substituted withone or more halogen groups, such as chlorine, bromine and iodine. Inthis manner, halogen containing groups can be substituted for thehydrolyzable groups attached to the silicon atom in the polymer therebyto increase the fire and chemical resistance properties of theinterpolymer that is produced. Representative of such halogenatedalcohols which may be used in the practice of this phase of theinvention are ROH compounds in which the R group is a halogenated,saturated or unsaturated, organic group of from one to 18 carbon atomsin the form of an aliphatic, aromatic, mixed aliphatic aromatic,heterocyclic and the like grouping, such ashexachloronorbornenylmethanol, 2,2,2-trichloroethanol and the like.

The following example is given by way of illustration of this concept ofthe invention:

EXAMPLE 6 The reaction of Example 4 was repeated except that 10 grams of1,2,3,4,7,7-hexachloronorbornene-2- methanol-5 was substituted for theallyl alcohol in the reaction with the formed interpolymer.

After purification and drying, the interpolymer gave a chlorine analysisof 0.59 percent by weight chlorine. The resulting interpolymer in theform of an elastomer could have a number of unique properties.

By way of further concept of this invention, the alcohol used tosubstitute the OR groups for the highly hydrolyzable group attached tothe silicon atom of the formed interpolymer may be an alcoholic orphenolic antioxidant whereby the OR group which becomes bound to theinterpolymer constitutes an antioxidant which now forms a part of therubber molecule or interpolymer. Such alcoholic or phenolic antioxidantsmay be represented by the general formula nmwumQ-on EXAMPLE 7 Thereaction is the same as that of Example 4 except that the allyl alcoholis substituted by 0.5 part by weight per parts by weight rubber of theantioxidant represented by the first of the above formulae in which R istertiary butyl and n is 1.

The interpolymer that is formed represents an elastomer having improvedoxidation resistance.

The interpolymers produced in accordance with Examples 3 through 7 canbe used as adhesives for metal, paper, plastics, rubber, natural orsynthetic fibers, or they may be used as films or binders for dyes,filaments, pigments, fillers and the like.

Secondary or tertiary alcohols for steric reasons are not effective forremoval of the highly hydrolyzable groups from the organo siliconsegment of the formed interpolymer. As a result, such secondary ortertiary alcohols can be used effectively to kill the catalyst withoutcausing significant post-jumping of the interpolymer to increasemolecular weight by crosslinking or loss of hydrolyzable SiX group.Representative of such secondary ortertiary alcohols are alcohols havingthe general formula R CHOH or R COH, in which R is a C -C straight orbranched chain, saturated or unsaturated, substituted or unsubstituted,alkyl or aryl group, such as isopropanol, sec-butanol, t-butanol and thelike. This can be illustrated by the following example.

EXAMPLE 8 It was noted in Example 1 that extreme gel formation tookplace almost immediately upon addition of the water. The polymerizationwas repeated but, instead of treating the polymer solution with water,one ml of dry isopropanol was added. It was observed that even uponprolonged agitation of the isopropanol-cement solution, no gel formed.However, upon subsequent coagulation of the polymer with steam and thedrying of the polymer, excessive crosslinking took place. Therefore, aconsiderable number of chlorine-silicon bonds must have remained afterthe isopropanol treatment to subsequently hydrolyze to give the siloxanecrosslinking. The polymer was very tough and would not press a smoothfilm in a Carver press at 180 C.

It has been found, in accordance with a further concept of thisinvention, that other high molecular weight compounds, polymers,copolymers or interpolymers containing a free amino and/or hydroxylgrouping can be grafted onto the interpolymer of this invention by wayof the highly hydrolyzable group attached to the silicon atom in thebackbone of the interpolymer whereby the amino or hydroxyl group reactsto hydrolyze off the hydrolyzable group and substitute the correspondinghigh molecular weight compound, polymer, copolymer or interpolymer as agraft onto the backbone of the interpolymer.

For example, the interpolymer containing the SiX grouping in the chaincan be interacted with cellulosic, alkyd, polyester, polyamide orpolyether fibers or resins for linking the latter molecular onto theinterpolymer by interaction between the SiX of the interpolymer with thehydroxyl or amino group of the fiber or resin as representedschematically by the following equation:

where R is cellulosic, polyester, etc., and R is a-olefin polymer.

Similarly, organo silicon polymers and copolymers in the form ofpolysiloxanes containing free hydroxyl groups such as SiOl-l may beinteracted with hydrolyzable groups attached to the silicon atom of theinterpolymer to graft the polysiloxane onto the interpolymer to form anintegral part thereof.

Similarly, polyethers having free hydroxyl groups as represented by theformula hydroxyl terminated polybutadienes as represented by the generalformula hydroxyl terminated polystyrene having the general formula orpolyurethanes having free hydroxyl or amino groups may be grafted ontothe interpolymer by replacement of highly hydrolyzable groups attachedto the silicon atom of the interpolymer.

By reason of the interaction between the interpolymer and the fibers orresins of cellulose, polyamide resins, polyester resins, alkyd resins,silicone resins, polyethers, polybutadiene, polystyrenes andpolyurethanes of the type described, it is possible to establish astrong and permanent interbonded relationship by reason of theinteraction between such high molecular weight polymeric or copolymericmaterials and the interpolymer.

EXAMPLE 9 A dry flask was first flushed with nitrogen gas and filledwith 100 cc of dry tetrachloroethylene, flushed with polymerizationgrade propylene and pressured to 14 psig with propylene. The flask wasbrought to 25 psig total molecular pressure by addition from a feed tankcontaining 65 mole percent ethylene and 35 mole percent propylene.Polymerization was carried out in a water bath maintained at 35 C.Addition was made to the flask of the following reactants: 0.4 mM5-ethylidene-2-norbornene, 0.03 mM butyl perchlorocrotonate, 0.04 mM ofpyridine, 0.375 mM norbornenyl trichlorosilane, 0.3 mM ethyl aluminumsesquichloride and 0.0075 mM vanadium oxytrichloride.

As the polymerization proceeded, the monomer composition in ethylene andpropylene was maintained constant by continuous addition from the feedtank. At 300 seconds and again at 600 seconds, the above reactants wereagain charged to the flask and at 900 seconds, 0.3 cc pyridine wasadded. The monomers were vented and the resulting cement was flushedwith nitrogen. The interpolymer, in solution in the cement, containedabout four carbon-to-carbon double bonds -C -C-) per 1000 carbon atoms.

Rayon cord was passed through the cement and then through a drying ovenat 400F. The rubber impregnated cord was pressed between two layers ofstandard EPDM rubber (EPsyn 40 of Copolymer Rubber & ChemicalCorporation), containing a sulphur system for cure. The composition wascured and standard H- adhesion tests were performed. An average of 16tests gave an l-l-adhesion value of 14.4.

An EPDM cement similar to the one above was prepared, but without thenorbornenyl trichlorosilane. The cement was post-treated and handledexactly as described above. An average 'of 11 pulls gave an H- adhesionvalue of 9.8.

In accordance with a further novel concept of the invention, it has beenfound that treatment of the interpolymer with a tertiary amine, such aspyridine, prior to interaction with the alcohol or with an anhydride,amine or phenol, as hereinafter described, is effective to increase theamount of substitution of the respective grouping for the hydrolyzablegroup that remains attached to the silicon atom of the formedinterpolymer. This unique concept for activation to increase the amountof substitution or graft can be illustrated by the following examples.

EXAMPLES 10-12 Three polymerizations were performed in the mannerdescribed in Example 4 except that each charge contained 0.03 mMbutylperchlorocrotonate, 0.04 mM pyridine, 0.375 mM norbornenyltrichlorosilane, 0.3 mM ethyl aluminum sesquichloride and 0.0075 mMvanadium oxytrichloride. The polymerization solutions were treated withdifferent levels of pyridine before treatment with 4 cc allyl alcoholand then subsequently 4 cc of methanol, with the following results:

Pyridine Level C=Cll000 C in Polymer 0.3 cc 0.9 cc

hydrolyzable group. That whichremains in the interpolymer mightinterfere with the use to be made of the interpolymer or effectundesirable reactions of the interpolymer such as crosslinking. Thus itis a further object of this invention to provide a means for effectingremoval of the remaining halogen or other hydrolyzable groups or toeffect their inactivation after the interpolymer has been treated withthe desired alcohol, amine, anhydride, or phenol to bring about thedesired substitution.

An important concept of this invention therefore resides in thestabilization of the interpolymer to prevent post-reaction stemming fromhydrolyzable groups remaining after the interpolymer has been treatedwith an alcohol or other compound for substitution of the hydrolyzablegroups attached to the silicon atom in the interpolymer. It has beenfound that post-treatment with methanol, or to a lesser extent with ahigher primary alcohol, will substantially effect complete removal ofany halogen or other hydrolyzable groups remaining in the interpolymerso that they will not be available for undesirable post-reactions and sothat the resulting compound will be stable.

The foregoing may be illustrated by the following examples:

EXAMPLE 13 The polymerization was carried out in the manner described inExample 4. After polymerizing for 900 seconds, the cement was treatedwith 0.33 cc of dry pyridine and 2 cc of hexachloronorbornenyl methanol.After shaking for 20 minutes, 5 cc of water and 0.05 gram of Irganox1010 were added. The cement was water washed and steam coagulated. Afterdrying in an oven at 80 C, the resulting polymer was found to beextremely tough and insoluble and incapable of being pressed into a filmin a hot Carver press.

EXAMPLE 14 The same polymerization was performed as in Example 13 but,in this example, 4 cc of methanol was added after the 20 minute exposureto the hexachloronorborncnyl methanol. After reacting 20 minutes withmethanol, the cement was treated as in Example 13. The resulting polymerwas soft, soluble in hexane and was capable of being pressed into asmooth thin film on a hot Carver press.

The foregoing indicates that without terminal treatment with methanol,the interpolymer still contained reactive chlorine groups whichpermitted cross polymerization when the interpolymer was subsequentlycontacted with water and/or steam for coagulation whereas such reactivechlorine groups were removed by the methanol in Example 14 to avoid theproblem of crosslinking to an insoluble polymer during the coagulationstep.

In the same manner, the polymer can be reacted with allyl alcohol forsubstitution of only a small portion of the halogen groups attached tothe silicon atoms of the interpolymer and then terminally reacting theproduct with methanol to remove the remaining halogens to produce arubber that will not pre-cure or crosslink, as in Example 13, so thatthe resulting elastomer can be processed in the usual manner andsubsequently cured.

In somewhat the same manner as the alcohol hydrolysis of halogensattached to the silicon atom of the formed interpolymer, the halogen orother hydrolyzable group can be replaced by interaction between theformed interpolymer and organic anhydride, primary or secondary aminecompounds, hydroxyl compounds such as phenols, and other active hydrogencontaining compounds having an active hydrogen group which is effectivein removing the halogen to form the corresponding hydrogen halide whilethe residue replaces the halogen formerly attached to the interpolymer.

In this manner chlorendic anhydride can be substituted for thehydrolyzable group into the interpolymer to improve flame resistance ofthe interpolymer; maleic anhydride or acetic anhydride can be tied intothe interpolymer to produce an elastomer having improved characteristicsand to provide an elastomer that can be further polymerized bycondensation polymerization.

Primary amines and ammonia inter-react in a manner similar to water tokill the catalyst and bring about the molecular jump by crosslinkingwhile secondary amines form addition products by substitution forhydrolyzable groups attached to the silicon atom, but do not effectcrosslinking.

The reaction with alcohol, anhydridcs or phenols appears to be catalyzedby tertiary amines, such as pyridine, as previously described, toincrease the amount of substitution. Instead of, or in addition to, thepyridine or other tertiary amine may function as scavengers for thehydrogen halide or other hydrolyzable group that is released upondetachment of the chlorine from the silicon atom.

The following example will illustrate the postreaction of theinterpolymer with an amine to effect substitution into the interpolymer:

EXAMPLE 15 A polymerization was carried out as described in Example 4.The polymerization was treated at 900 seconds with 4 cc of dry diphenylamine. After 20 minutes of shaking, the cement-amine solution wasfurther treated with 4 cc of methanol. After 20 minutes, 1 cc of waterand 0.005 gram of Irganox 1010 was added. The cement was washed withwater and steam coagulated. The resulting polymer was purified byredissolving in hexane and coagulating with isopropanol. The polymer wasdried in a vacuum at C to yield a product containing 0.086 percent byweight nitrogen as determined by elemental analysis. This is equivalentto an incorporation of 0.86 moles of diphenyl amine per 1,000 carbonatoms.

Such modified interpolymers should be more highly receptive to dyecoloring by comparison with the same interpolymer without the attachedamine groups.

Similar concepts relying on interaction between hydroxyl or amino groupswith highly hydrolyzable groupings attached to the silicon atom of theinterpolymer can be used to include into the interpolymer certain dyecompounds having free hydroxyl groups as repre- When tied in to form apart of the molecule, such dye compounds operate permanently to impartdye color to the interpolymer that is formed. The color resists re-.moval by washing or drycleaning.

CONCLUSION It will be apparent from the foregoing that we have provideda new and novel interpolymer and method for the preparation of same andan interpolymer which is capable of numerous modifications by reactionwith components thereof to produce new and novel products and methodsfor the preparation of same.

It will be understood that changes may be made in the details offormulation and operation without departing from the spirit of theinvention, especially as defined in the following claims.

We claim:

1. An interpolymer which is the product of the interpolymerization of anethylenically unsaturated organosilane having the general formula R,.SiXin which X is a highly hydrolyzable group which does not contain anoxygen group, R is a group selected from the group consisting ofhydrogen, alkyl, aryl, alkaryl, arylalkyl, cyclic or heterocyclic groupin which at least one of the R groups contains an unsaturated carbon tocarbon linkage and an olefin selected from the group consisting of 1)ethylene, (2) a monoolefin having from three to carbon atoms and (3) apolyene andmixtures thereof in which at least ethylene is present as amonomer, in which at least one hydrolyzable X group remains attached tothe silicon atom in the product that is formed, and in which at leastone of the remaining hydrolyzable X groups is replaced by a nucleophilicgroup substituted therefor after the product is formed.

2..An interpolymer as claimed in claim 1 which includes at least onemonoolefin having from three to 20 carbon atoms.

3. An interpolymer as claimed in claim 1 which includes a polyene.

4. An interpolymer as claimed in claim 1 in which the olefinic monomersinclude ethylene, at least one monoolefin containing three to 20 carbonatoms, and a polyene.

5. An interpolymer as claimed in claim 1 in which the unsaturated organosilane is selected from the group consisting of the vinyl, allyl,crotyl, divinyl, diallyl, dicrotyl and styryl trihalo and dihalosilanes. 6. An interpolymer as claimed in claim 1 in which theunsaturated group of the unsaturated organo silane is a norbornenylgroup.

7. An interpolymer as claimed in claim 1 in which the monoolefin ispropylene.

8. An interpolymer as claimed in claim 1 in which the polyene is apolyunsaturated bridged ring hydrocarbon or a halogenatedpolyunsaturated bridged ring hydrocarbon.

9. An interpolymer as claimed in claim 8 in which the polyene is analkylidene-norbornene.

10. An interpolymer as claimed in claim 9 in which thealiylidene-norbornene is 5-ethylidene-2- norbornene.

11. An interpolymer as claimed in claim 1 in which the hydrolyzable Xgroups attached to the silicon atoms in the product are replaced by ORgroups of an alcohol.

12. An interpolymer as claimed in claim 1 in which the hydrolyzable Xgroups attached to the silicon atoms in the product are replaced byhalogenated alkoxy groups.

13. An interpolymer as claimed in claim 1 in which the hydrolyzable Xgroups attached to the silicon atoms in the product are replaced by dyegroups to produce a permanently colored interpolymer.

14. An interpolymer as claimed in claim 1 in which any residualhydrolyzable X groups remaining after the primary post-reaction arereplaced by alkoxy groups.

15. The method which comprises the interpolymerization in solventsolution in the presence of a Ziegler type catalyst of an ethylenicallyunsaturated organo silane having the general formula R,,SiX in which Xis a highly hydrolyzable group other than an oxygen containing group, Ris a group selected from the group consisting of hydrogen, alkyl, aryl,alkaryl, arylalkyl, cyclic or heterocyclic group in which at least oneof the R groups contains an unsaturated carbon to carbon linkage, andolefinic monomers selected from the group consisting of (1) ethylene,(2) a monoolefin having from three to 20 carbon atoms and (3) a polyene,but in which at least ethylene is present as a monomer, and in whichwhere both ethylene and the monoolefin are present the ethylene andmonoolefin are present in the mole ratio of 20-95 moles ethylene to -5moles monoolefin, and when the polyene is present the polyene is presentin an amount within the range of 0.1 to 10 mole percent and theunsaturated organo silane is present in an amount within the range of0.1 to 10 percent by weight, and then reacting the product to effectsubstitution of a nucleophilic group for at least one of thehydrolyzable X groups which remains attached to the silicon atoms in theinterpolymer that is formed.

16. The method as claimed in claim 15 in which the monoolefin ispropylene and in which the ethylene and propylene are reacted in theinterpolymerization mixture in the ratio of 45-90 moles of ethylene to55-10 moles of propylene, the polyene is present in an amount within therange of 0.1 to 3 moles and the unsaturated organosilane is present inan amount within the range of l to 5 percent by weight.

17. The method as claimed in claim 15 in which the unsaturatedorganosilane is selected from the group consisting of the vinyl, allyl,crotyl, divinyl, diallyl, dicrotyl and styryl trihalo and dihalosilanes.

18. The method as claimed in claim 15 in which the unsaturated group ofthe organosilane compound is a norbornenyl group.

19. The method as claimed in claim 15 in which the olefmic monomercomprises both ethylene and polyene.

20. The method as claimed in claim 15 in which the olefinic monomerscomprise ethylene and at least one monoolefin.

21. The method as claimed in claim 15 in which the product is reactedwith an alcohol to replace hydrolyzable X groups attached to siliconatoms in the interpolymer with organic OR groups of the alcohol.

22. The method as claimed in claim 21 in which the alcohol is anunsaturated alcohol which increases the amount of unsaturation in theformed interpolymer.

23. The method as claimed in claim 21 in which the alcohol is ahalogenated alcohol.

of hydrolyzable groups attached to the silicon atom of the formedinterpolymer before reacting the interpolymer for replacement ofhydrolyzable groups attached to the silicon atom.

27. The method as claimed in claim 15 which includes the step of furtherreacting the reaction product with a primary alcohol to hydrolyze offany hydrolyzable X groups that remain attached to the silicon atoms ofthe interpolymer after the first post-reaction.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,764,589 Dated October 7 Inventor(s) Wll'llam BQnd, Jr. t al.

that error appears in the above-identified patent It is certified ycorrected as shown below:

and that said Letters Patent are hereb line 6, change "6-isopropy1idene"line 7, change 5-is0buty1idene;

co1um4, line 38, cancel 3,093,621; line 39, change No. 2, 113,115

to NO. 3 113 115 Signed and sealed this 16th day of April 197b,.

(SEAL) At'test:

EDWARD I-LFLETCHERJR. C. MARSHALL DAMN Attesting Officer Commissioner ofPatents USCOMM'DC 603764 69 U.$. GOVERNMENT PIINT NG OFHCl: I9!O-lfl-SJA "ORM PO-l 050 (10-69)

2. An interpolymer as claimed in claim 1 which includes at least onemonoolefin having from three to 20 carbon atoms.
 3. An interpolymer asclaimed in claim 1 which includes a polyene.
 4. An interpolymer asclaimed in claim 1 in which the olefinic monomers include ethylene, atleast one monoolefin containing three to 20 carbon atoms, and a polyene.5. An interpolymer as claimed in claim 1 in which the unsaturated organosilane is selected from the group consisting of the vinyl, allyl,crotyl, divinyl, diallyl, dicrotyl and styryl trihalo and dihalosilanes.
 6. An interpolymer as claimed in claim 1 in which theunsaturated group of the unsaturated organo silane is a norbornenylgroup.
 7. An interpolymer as claimed in claim 1 in which the monoolefinis propylene.
 8. An interpolymer as claimed in claim 1 in which thepolyene is a polyunsaturated bridged ring hydrocarbon or a halogenatedpolyunsaturated bridged ring hydrocarbon.
 9. An interpolymer as claimedin claim 8 in which the polyene is an alkylidene-norbornene.
 10. Aninterpolymer as claimed in claim 9 in which the aliylidene-norbornene is5-ethylidene-2-norbornene.
 11. An interpolymer as claimed in claim 1 inwhich the hydrolyzable X groups attached to the silicon atoms in theproduct are replaced by OR groups of an alcohol.
 12. An interpolymer asclaimed in claim 1 in which the hydrolyzable X groups attached to thesilicon atoms in the product are replaced by halogenated alkoxy groups.13. An interpolymer as claimed in claim 1 in which the hydrolyzable Xgroups attached to the silicon atoms in the product are replaced by dyegroups to produce a permanently colored interpolymer.
 14. Aninterpolymer as claimed in claim 1 in which any residual hydrolyzable Xgroups remaining after the primary post-reaction are replaced by alkoxygroups.
 15. The method which comprises the interpolymerization insolvent solution in the presence of a Ziegler type catalyst of anethylenically unsaturated organo silane having the general formulaRnSiX4 n in which X is a highly hydrolyzable group other than an oxygencontaining group, R is a group selected from the group consisting ofhydrogen, alkyl, aryl, alkaryl, arylalkyl, cyclic or heterocyclic groupin which at least one of the R groups contains an unsaturated carbon tocarbon linkage, and olefinic monomers selected from the group consistingof (1) ethylene, (2) a monoolefin having from three to 20 carbon atomsand (3) a polyene, but in which at least ethylene is present as amonomer, and in which where both ethylene and the monoolefin are presentthe ethylene and monoolefin are present in the mole ratio of 20-95 molesethylene to 80-5 moles monoolefin, and when the polyene is present thepolyene is present in an amount within the range of 0.1 to 10 molepercent and the unsaturated organo silane is present in an amount withinthe range of 0.1 to 10 percent by weight, and then reacting the productto effect substitution of a nucleophilic group for at least one of thehydrolyzable X groups which remains attached to the silicon atoms in theinterpolymer that is formed.
 16. The method as claimed in claim 15 inwhich the monoolefin is propylene and in which the ethylene andpropylene are reacted in the interpolymerization mixture in the ratio of45-90 moles of ethylene to 55-10 moles of propylene, the polyene ispresent in an amount within the range of 0.1 to 3 moles and theunsaturated organosilane is present in an amount within the range of 1to 5 percent by weight.
 17. The method as claimed in claim 15 in whichthe unsaturated organosilane is selected from the group consisting ofthe vinyl, allyl, crotyl, divinyl, diallyl, dicrotyl and styryl trihaloand dihalo silanes.
 18. The method as claimed in claim 15 in which theunsaturated group of the organosilane compound is a norbornenyl group.19. The method as claimed in claim 15 in which the olefinic mOnomercomprises both ethylene and polyene.
 20. The method as claimed in claim15 in which the olefinic monomers comprise ethylene and at least onemonoolefin.
 21. The method as claimed in claim 15 in which the productis reacted with an alcohol to replace hydrolyzable X groups attached tosilicon atoms in the interpolymer with organic OR groups of the alcohol.22. The method as claimed in claim 21 in which the alcohol is anunsaturated alcohol which increases the amount of unsaturation in theformed interpolymer.
 23. The method as claimed in claim 21 in which thealcohol is a halogenated alcohol.
 24. The method as claimed in claim 15in which the post-reaction comprises adding a secondary or tertiaryalcohol to the solution following polymerization to kill the catalystwhile still leaving hydrolyzable groups attached to the silicon atom inthe interpolymer.
 25. The method as claimed in claim 15 in which theinterpolymer is reacted with a dyestuff having free amino or hydroxylgroups to substitute the dye group for hydrolyzable groups attached tothe silicon atoms.
 26. The method as claimed in claim 15 which includesthe step of killing the catalyst without removal of hydrolyzable groupsattached to the silicon atom of the formed interpolymer before reactingthe interpolymer for replacement of hydrolyzable groups attached to thesilicon atom.
 27. The method as claimed in claim 15 which includes thestep of further reacting the reaction product with a primary alcohol tohydrolyze off any hydrolyzable X groups that remain attached to thesilicon atoms of the interpolymer after the first post-reaction.